Catalytic composition and its preparation and use for preparing polymers from ethylenically unsaturated monomers

Abstract

A catalytic composition, including a cationic metal-pair complex, is disclosed, along with a method for its preparation. A method for the polymerization of ethylenically unsaturated monomers using the catalytic composition, and the addition polymers produced thereby are also disclosed.

1. A catalytic composition comprising at least one cationic metal-pair complex, wherein:
 said cationic metal-pair complex comprises at least one metal atom pair, said pair comprising a first metal atom, M 1 , and a second metal atom, M 2 ; 
 said first metal atom and said second metal atom of said pair have a through-space internuclear distance of at least 1.5 Angstroms and no more than 20 Angstroms; and 
 said cationic metal-pair complex is a complex according to formula I, 
 
       
         
           
           
               
               
           
         
          wherein:
 M 1  represents a first metal atom selected from copper, iron, cobalt, ruthenium, rhodium, chromium, and manganese; 
 L 1  represents a set of first ligands; 
 L 2  represents a set of second ligands; 
 L 3  represents a set of third ligands; 
 R 1  represents a set of first anionic hydrocarbyl containing radicals; 
 R 2  represents a set of second anionic hydrocarbyl containing radicals; 
 S 1  represents a set of first labile ligands; 
 S 2  represents a set of second labile ligands; 
 A 1 –A 8  each represent a set of coordination bonds; 
 WCA represents a weakly coordinating anion; 
 a, b, h, k, m, and p are each selected from 0 and 1; 
 α, β, and c each equal 1; 
 d, r, and t are each selected from 0, 1, 2, 3, 4, and 5; 
 f is selected from 1, 2, 3, 4, 5, and 6; 
 1≦m+p≦2; 
 the sum d+f+r+t=6; and 
 sum e+g+s+u=4, 5, or 6; and 
 wherein:
 when the sum e+g+s+u=4,
 M 2  represents a second metal atom selected from nickel, palladium, copper, iron, cobalt, rhodium, chromium, and manganese; 
 e, s, and u are each selected from 0, 1, 2, and 3; 
 g is selected from 1, 2, 3, and 4; 
 0≦d+e≦7; 1≦r+s≦7; 0≦t+u≦7; and 2≦f+g≦9; or 
 
 when the sum e+g+s+u=6,
 M 2  represents a second metal atom selected from copper, iron, cobalt, ruthenium, rhodium, chromium, and manganese; 
 e, s, and u are each selected from 0, 1, 2, 3, 4, and 5; 
 g is selected from 1, 2, 3, 4, 5, and 6; 
 0≦d+e≦9; 1≦r+s≦9; 0≦t+u≦9; and 2≦f+g≦11. 
 
 
 
       
     
     
       2. The catalytic composition of  claim 1 , wherein said first metal atom and said second metal atom of said pair have a through-space internuclear distance of at least 2 Angstroms and no more than 10 Angstroms. 
     
     
       3. The catalytic composition of  claim 1 , wherein at least one of said first anionic hydrocarbyl containing radicals and said second anionic hydrocarbyl containing radicals is an addition polymer. 
     
     
       4. A method for preparing a catalytic composition, comprising:
 (i) providing a full-(metal pair) precursor complex according to said formula II 
 
       
         
           
           
               
               
           
         
          wherein:
 M 1  represents a first metal atom selected from copper, iron, cobalt, ruthenium, rhodium, chromium, and manganese; 
 L 1  represents a set of first ligands; 
 L 2  represents a set of second ligands; 
 L 3  represents a set of third ligands; 
 R 1  represents a set of first anionic hydrocarbyl containing radicals; 
 R 2  represents a set of second anionic hydrocarbyl containing radicals; 
 S 1  represents a set of first labile ligands; 
 S 2  represents a set of second labile ligands; 
 A 1 –A 10  each represents a set of coordination bonds; 
 Y represents a leaving group; 
 d+f+r+t+x=6; and 
 the sum e+g+s+u+y=4, or 6; 
 
         (ii) combining said full-(metal pair) precursor complex with at least one activator component; 
         (iii) removing said leaving group Y from said full-(metal pair) precursor complex; and 
         (iv) replacing said leaving group Y with at least one replacement moiety; 
         wherein for said full-(metal pair) precursor complex
 α, β, and c each equal 1; 
 a, b, h, k, m, p, x, and y are each selected from 0 and 1; 
 d, r, and t are each selected from 0, 1, 2, 3, 4, and 5; 
 f is selected from 1, 2, 3, 4, 5, and 6; 
 1≦m+p≦2; and 
 1≦x+y≦2; 
 
          wherein:
 when the sum e+g+s+u+y=4,
 M 2  represents a second metal atom selected from nickel, palladium, copper, iron, cobalt, rhodium, chromium, and manganese; 
 e, s, and u are selected from 0, 1, 2, and 3; 
 g is selected from 1, 2, 3, and 4; 
 0≦d+e≦6; 1≦r+s≦7; 0≦t+u≦6; and 2≦f+g≦8; or 
 
 when the sum e+g+s+u+y=6,
 M 2  represents a second metal atom selected from copper, iron, cobalt, ruthenium, rhodium, chromium, and manganese; 
 e, s, and u are each selected from 0, 1, 2, 3, 4, and 5; 
 g is selected from 1, 2, 3, 4, 5, and 6; 
 0≦d+e≦8; 1≦r+s≦9; 0≦t+u≦8; and 2≦f+g≦10. 
 
 
       
     
     
       5. A method for preparing a catalytic composition, comprising:
 (i) providing a first semi-(metal pair) precursor complex and a second semi-(metal pair) precursor complex both according to formula II 
 
       
         
           
           
               
               
           
         
          wherein:
 M 1  represents a first metal atom selected from copper, iron, cobalt, ruthernium, rhodium, chromium, and manganese; 
 L 1  represents a set of first ligands; 
 L 2  represents a set of second ligands; 
 L 3  represents a set of third ligands; 
 R 1  represents a set of first anionic hydrocarbyl containing radicals; 
 R 2  represents a set of second anionic hydrocarbyl containing radicals; 
 S 1  represents a set of first labile ligands; 
 S 2  represents a set of second labile ligands; 
 A 1 –A 10  each represents a set of coordination bonds; 
 Y represents a leaving group; 
 
         (ii) combining said first semi-(metal pair) precursor complex with at least one activator component; 
         (iii) removing said leaving group Y from said first semi-(metal pair) precursor complex; and 
         (iv) replacing said leaving group Y with said second semi-(metal pair) precursor complex; 
         wherein for said first semi-(metal pair) precursor complex
 α and x each equal 1; 
 β, b, c, k, p, e, f, g, s, u, and y each equal 0; 
 a, h, and m are each selected from 0 and 1; 
 d, r, and t are each selected from 0, 1, 2, 3, 4, and 5; and 
 the sum d+f+r+t+x=6; and 
 
         wherein for said second semi-(metal pair) precursor complex
 β equals 1; 
 α, a, c, h, m, d, f, g, r, t, x, and y each equal 0; 
 b, k, and p are each selected from 0 and 1; and 
 the sum e+g+s+u+y=4, or 6; and 
 wherein:
 when the sum e+g+s+U+y=4,
 M 2  represents a second metal atom selected from nickel, palladium, copper, iron, cobalt, rhodium, chromium, and manganese; 
 e is selected from 0, 1, 2, 3, and 4; and 
 s and u are each selected from 0, 1, 2, and 3; or 
 
 when the sum e+g+s+u+y=6
 M 2  represents a second metal atom selected from copper, iron, cobalt, ruthenium, rhodium, chromium, and manganese; 
 e is selected from 0, 1, 2, 3, 4, 5, and 6; and 
 s and u are each selected from 0, 1, 2, 3, 4, and 5; and 
 
 
 
         wherein the sum of m of said first semi-(metal pair) precursor complex+p of said second semi-(metal pair) precursor complex is selected from 1 or 2. 
       
     
     
       6. A method for preparing a catalytic composition, comprising:
 (i) providing a first semi-(metal pair) precursor complex and a second semi-(metal pair) precursor complex both according to formula II 
 
       
         
           
           
               
               
           
         
          wherein:
 M 1  represents a first metal atom selected from copper, iron, cobalt, ruthenium, rhodium, chromium, and manganese; 
 L 1  represents a set of first ligands; 
 L 2  represents a set of second ligands; 
 L 3  represents a set of third ligands; 
 R 1  represents a set of first anionic hydrocarbyl containing radicals; 
 R 2  represents a set of second anionic hydrocarbyl containing radicals; 
 S 1  represents a set of first labile ligands; 
 S 2  represents a set of second labile ligands; 
 A 1 –A 10  each represents a set of coordination bonds; 
 Y represents a leaving group; 
 
         (ii) combining said first semi-(metal pair) precursor complex with at least one activator component; 
         (iii) removing said leaving group Y from said first semi-(metal pair) precursor complex; and 
         (iv) replacing said leaving group Y with said second semi-(metal pair) precursor complex; 
         wherein for said first semi-(metal pair) precursor complex
 β and y each equal 1; 
 α, a, c, h, m, d, f, g, r, t, and x each equal 0; 
 b, k, and p are each selected from 0 and 1; and 
 the sum e+g+s+u+y=4, or 6; and 
 wherein:
 when the sum e+g+s+u+y=4,
 M 2  represents a second metal atom selected from nickel, palladium, copper, iron, cobalt, rhodium, chromium, and manganese; and 
 e, s and u are each selected from 0, 1, 2, and 3; 
 
 when the sum e+g+s+U+y=6
 M 2  represents a second metal atom selected from copper, iron, cobalt, ruthenium, rhodium, chromium, and manganese; and 
 e, s and u are each selected from 0, 1, 2, 3, 4, and 5; and 
 
 
 
         wherein for said second semi-(metal pair) precursor complex
 α equals 1; 
 β, b, c, k, p, e, f, g, s, u, x, and y each equal 0; 
 a, h, and m are each selected from 0 and 1; 
 d is selected from 0, 1, 2, 3, 4, 5, and 6; 
 r and t are each selected from 0, 1, 2, 3, 4, and 5; and 
 the sum d+f+r+t+x=6; and 
 
         wherein the sum of m of said first semi-(metal pair) precursor complex+p of said second semi-(metal pair) precursor complex is selected from 1 or 2. 
       
     
     
       7. A method for preparing at least one addition polymer comprising:
 (a) combining:
 (i) a catalytic composition according to  claim 1 ; and 
 (ii) at least one ethylenically unsaturated monomer; and 
 
 (b) polymerizing said at least one ethylenically unsaturated monomer in the presence of said catalytic composition to form said addition polymer. 
 
     
     
       8. The method of  claim 7 , wherein said at least one addition polymer is selected from poly[(polar olefin)-(non-polar olefin)], poly(polar olefin), poly(non-polar olefin), and combinations thereof, wherein said at least one said ethylenically unsaturated monomer is selected from at least one polar olefinic monomer, at least one non-polar olefinic monomer, and combinations thereof. 
     
     
       9. The method of  claim 8 , wherein said poly[(polar olefin)-(non-polar olefin)] has a combined molar percentage of polar olefinic monomers and non-polar olefinic monomers present, as polymerized units, of at least 70 mole-% to 100 mole-%, based upon the total moles of all polar olefinic monomers and non-polar olefinic monomers present, as polymerized units, in said at least one addition polymer. 
     
     
       10. The method of  claim 7 , wherein said addition polymer comprises, as polymerized units, at least one (meth)acrylate monomer, wherein said (meth)acrylate monomers have a molar ratio to all said ethylenically unsaturated monomers, present as polymerized units, of at least 0.05:99.95 to 100:0. 
     
     
       11. The method of  claim 7 , wherein said addition polymer comprises, as polymerized units, at least one cyclic olefin monomer, wherein said cyclic olefin monomers have a molar ratio to all said ethylenically unsaturated monomers, present as polymerized units, of at least 0.05:99.95 to 100:0.